Polyamide fiber dyed with disazo-dyestuffs

ABSTRACT

Compounds of the formula   WHEREIN A is hydrogen, lower alkyl such as methyl, ethyl or propyl, lower alkoxy such as methoxy, ethoxy or butoxy, or chlorine; B and B1 are hydrogen, lower alkyl such as methyl, ethyl or butyl, or lower alkoxy such as methoxy, ethoxy, or butoxy; E is hydrogen, lower alkyl such as methyl, ethyl or butyl, or lower alkoxy such as methoxy, ethoxy or butoxy; R is hydrogen, methyl or chlorine and IS EITHER ORTHO OR PARA TO THE AZO LINKAGE; AND SO3H is either meta or para to the azo linkage, provide yellow to scarlet shades of good fastness and dyeing properties and excellent leveling characteristics on natural and synthetic polyamide fibers.

United States Patent Stingl [54] POLYAMIDE FIBER DYED WITH DISAZO-DYESTUFFS Primary Examiner-George F. Lesmes Assistant Examiner-Patricia C. Ives Attorney-Harry Goldsmith, Joseph G. Kolodny, Bryant W. Brennan and Edward J. Sites ethoigygr bUIOXLEjEllYdI'OgElI. lower alkyl such as net 51' 3,637,338 51 Jan. 25, 1972 [51] ABSTRACT Compounds of the formula A ill l N=N- N=N 1101s E B wherein A "i' ayaragen; ibwer alkyl suclias niethyl, ethyl or propyl, lower alkoxy such as methoxy, ethoxy or butoxy,

gr chlorine; B and B are Mgiroggg lgwer alkyl such as methyf etliyTor butyl, or lower alkoxy such as methoxy, bvh

or lower alkoxy such as met v ethyl or butyl,

hoxy, ethoiry or lautgxy; R i s hydrogen, methyl or chlorine and i is either ortho or para to the azo linkage, and SO3H is either meta or para to the azo linkage, provide yellow to scarlet s a es 0 goo astness an leveling characteristics on natural and synthetic polyamide fibers.

H l Clalrns, No Drawings yemgpropemes an exce ent POLYAMIDE FIBER DYED WITH DISAZO-DYESTUFFS This application is a divisional application of Ser. No. 743,630, filed July 10, 1968.

BACKGROUND OF THE INVENTION The use of monoazo-dyestufis containing a sulfonic acid group for the dyeing of animal fibers and artificial fibers of superpolyamides or superpolyurethanes is known. However, the dyeing of nylon presents particular problems in obtaining good leveling and the achievement of optimum leveling is a very important consideration in the dyeing or printing of nylon in order to cover up irregularities.

SUMMARY OF THE INVENTION The present invention relates to and has for its objects the provision of dyestuffs particularly suited for the coloring of nylon fibers.

. In accordance with the present invention it has been found that valuable dyeings are obtained on natural and synthetic polyamide fibers by the use as dyestuffs of disazo compounds of the formula A B1 1 l s 02R II 0 a S E i wherein A is hydrogen, lower alkyl such as methyl, ethyl or propyl, lower alkoxy such as methoxy, ethoxy or butoxy, or chlorine; B and B are hydrogen, lower alkyl such as methyl, ethyl or butyl, or lower alkoxy such as methoxy, ethoxy or butoxy; E is hydrogen, lower alkyl such as methyl, ethyl or butyl, or lower alkoxy such as methoxy, ethoxy or butoxy; R is hydrogen, methyl or chlorine and is either ortho or para to the azo linkage; and SO H is either m t w wei hs az hkes t The dyestuffs of the present invention can be employed in the form of their salts, for example, in the form of the ammonium or alkali metals, such as sodium, potassium or lithium salts.

The disazo-dyestuffs of the present invention can be used for dyeing or printing a very wide variety of materials, principally for dyeing animal fibers such as leather, silk and especially wool and for dyeing artificial fibers of superpolyamides or superpolyurethanes. The dyeings obtainable therewith are distinguished by the purity and brightness of their tints, by excellent properties of fastness to alkali, light and washing and by dng evdltansfsLpwy r. W

The dyes of the present invention show very good exhaustion from a neutral dye-bath and provide dyeings over a shade range from yellow to orange.

The dyes will also dye well in combination, especially with the use of a leveling agent. If desired, a conventional aftertreatment can be given to the dyed material.

The following examples illustrate the invention.

. were? added t sh e qt zetienatwefii EXAMPLE 1 A. 17.3 grams of metanilic acid are dissolved in 70 grams of water by addition of 8 grams of 50 percent by weight caustic soda solution. Ice, 22 grams of concentrated hydrochloric acid, and a solution of 7 grams of sodium nitrite in 20 grams of B. 15.3 grams of 2,5-dimethoxyaniline, dissolved at 45 C. in 120 grams of water and 11 grams of concentrated hydrochloric acid, are combined with the diazotized metanilic acid and enough ice to keep the temperature below 5 C. and the pH is raised to 2.5 with 20 percent soda ash solution. After completion of the coupling, the product is dissolved at pH 9 with 50 percent caustic soda solution and then salted with 50 grams of sodium chloride. Rediazotization is accomplished by addition of 7.5 grams of sodium nitrite followed by an aqueous solution of 21 grams of naphthalene-sulfonic acid and sufficient sulfuric acid to establish a congo acid reaction. A temperature of 32 C. is maintained for 2 hours.

C. This reaction mass is added during 1 hour to a solution of 9.4 grams of phenol, 3 grams of caustic soda, and 25 grams of soda ash in 200 grams of water while the temperature is held below 5 C. by addition of ice.

The resulting slurry is stirred for 2 hours, neutralized with hydrochloric acid, and filtered.

D. The filter cake is dissolved in 500 grams of water at C., containing 4 grams of caustic soda and 5 grams of soda ash. Twenty grams of crushed p-toluenesulfochloride are added and the thickening reaction mass is stirred for 30 minutes at 8085 C. The pH is raised to 10 with caustic soda and the product is isolated by filtration. The filter cake is washed with 1 percent brine and dried to give a product of the few-.. a...

OCH;

saNa ()CH:

The product dyes nylon from neutral or weakly acid dye baths bright orange shades of good light and wash fastness properties.

EXAMPLE 2 The procedure of example 1 is repeated replacing the phenol in example 1 with 12.4 grams of meta-methoxyphenol, yielding a product of the structure:

S OaNa $0113 CH The product dyes nylon reddish-orange shades of good light and wash fastness.

EXAMPLE 3 17.3 grams by weight of nietanilic acid are diazotized by the procedure of example 1A. I

13.7 grams of 2-methoxy-5-methylaniline, dissolved at 45 C. in grams of water and 11 grams of concentrated hydrochloric acid are combined with the diazotized metanilic acid and enough ice to keep the temperature below 5 C. The pH is then gradually raised to 3.0 with 20 percent soda ash solution. The coupling product is filtered off the next morning 7 and subsequently dissolved in 500 grams of water at 50 C. by

addition of 8 grams of 50 percent by weight caustic soda solution. The solution is salted'with 28 grams of sodium chloride and cooled to 20 C. 7.2 grams of sodium nitrite are added, followed by an aqueous solution of 2i grams of naphthalenesulfonic acid and sufficient sulfuric acid to establish a congo acid reaction. One hour later an amount of sodium chloride (in weight units) equivalent to 20 percent of the volume of the slurry is added and the slurry is cooled to 8 C.

The precipitate is collected by filtration, reslurried in 250 grams of cold water and added during 1 hour to a solution of 9.4 grams of phenol, 3 grams of caustic soda and 20 grams of soda ash in 200 grams of water while holding the temperature below 5 C. by addition of ice and maintaining a sandy form by addition of 70 grams of sodium chloride. Two hours later the coupling product is isolated by filtration.

Tosylation of the filter cake is carried out as described in example lD.

The product isolated has the formula OCH;

and dyes nylon clear level shades of EXAMPLE 4 l7.3 grams of sulfanilic acid are diazotized in 50 grams of ice water and 11 grams of concentrated hydrochloric acid by the rapid addition of a concentrated solution of 7 grams of sodium nitrite in water at to 8 C. The diazotized sulfanilic acid is combined with 13.7 grams of 2-methoxy-5- methylaniline as described in example 3. The coupling product is acidified with hydrochloric acid the next morning and isolated by filtration. The filter cake is dissolved at pH 8.0 in 250 grams of water at 50 C. with caustic soda. Ten grams of sodium naphthalenesulfonate and 7 grams of sodium nitrite are added. The total preparation is gradually added to 200 grams of cold water containing 45 grams of concentrated hydrochloric acid and stirred for 1 hour at 30 C. it is then added during 1 hour to a solution of 9.4 grams of phenol, 6 grams of caustic soda, and 25 grams of soda ash in 200 grams of water while the temperature is held below C. by addition of ice. The resulting slurry is stirred for 2 hours, salted with I grams of sodium chloride, and filtered.

The filter cake is tosylated as described in example ID. The product obtained has the formula (Full;

and dyes nylon yellow-orange shades of good light and wash fastness.

EXAMPLE 5 17.3 grams of metanilic acid are diazotized by the procedure of example 1A. The pH of the resulting solution is then raised to 2.5 with sodium bicarbonate; 6.6 grams of sodium acetate are added, followed quickly by 22.5 grams of oanisidyl-N-methane-sulfonic acid while the temperature is held at 57 C. by adding ice and cold water. After stirring for l hour, 38 grams of 50 percent by weight caustic soda solution is added and the mass heated at 100 C. for 8 hours. It is then cooled, its pH reduced below 10.0 with 28 grams of sodium bicarbonate, salted with 33 grams of sodium chloride, and filtered.

Quia

The filter cake is dissolved neutral in 800 grams of water at 30 C. To the solution are added 7 grams of sodium nitrite followed by an aqueous solution of 2l grams of naphthalene-sulfonic acid and sufficient sulfuric acid to establish a congo acid reaction. A temperature of 32 C. is maintained for 2 hours. This reaction mass is combined with phenol as described in example IC. The tosylation procedure of example 1D is followed with the isolated intermediate product. The product obtained has the formula S OsNti.

and dyes nylon bright reddish-yellow of very good light and wash fastness.

Following the procedure set forth in example I and employing the appropriate end couplers, the following compounds providing reddish-orange shades of good light and wash fastsssa e 9b in The following examples illustrate further-but by no means limit-the scope of this invention:

EXAMPLE 9 NaOaS O-S Oi yellow EXAMPLE 10 OCH:

EXAMPLE 24 v A I U H or 0011, W M 0,3 p:

H O wherein A is hydrogen, lower alkyl, lower alkoxy or chlorine, B and B are hydrogen, lower alkyl or lower alkoxy, E is 10 hydrogen, lower alkyl or lower alkoxy, R is hydrogen, methyl N Mddlmomngo or chlorine, the group x mm w I H I '7 V V i V I is ortho or para to the am linkage and their alkali metal and lclaim: NH salts' and the group S0,H is meta or para to the azo l. Polyamide fiber dyed with a compound of the formula linkage.

M1 NH-Mm 

